Diaminoanthraquinones and their use as human hair dyes



United States Patent Tee 3,401,003 DIAMINOANTHRAQUIN ONES AND THEIR USEAS HUMAN HAIR DYES Karl-Josef Boosen, Dusseldorf-Holthausen, and GiinterReese, Dusseldorf, Germany, assignors t0 Therachemie ChemischTherapeutische Gesellscllaft m.b.H., Dusseldorf, Germany N0 Drawing.Filed Aug. 27, 1964, Ser. No. 392,607 Claims priority, appli$tg2nGermany, Sept. 4, 1963,

5 Claims. 61. s-10.1

ABSTRACT OF THE DISCLOSURE The invention relates to agents for dyeing ofhuman hair and, more particularly, to certain substituted anthraquinonedyes, as hereinafter will become more apparent. These dyes have theadvantage that they can be employed substantially at room temperature.

The use of certain anthraquinone derivatives for the dyeing of humanhair is known. These derivatives contain, e.g., amino-, hydroxyl-,carboxylor sulfo groups in the nucleus.

In the practical application of these known compounds it becomesnecessary to accomplish the dyeing of the hair at temperatures rangingfrom 40 to 60 C. Hence, heating caps or similar devices must be employedon the hair. It has also been established that the strength of thesedyes diminishes greatly when they are incorporated in creams or pastes,as frequently is the case in practice.

It now has been found that hair dyeing agents containing anthraquinonecompounds as described hereinafter in detail, surprisingly do notexhibit the above-named drawbacks. The novel hair dyes are characterizedby a content of anthraquinone compounds which are free of acid groups inthe nucleus and which contain a side chain consisting of a hydrocarbonradical connected to the nucleus by way of an oxygen or nitrogen atom,this hydrocarbon radical further containing a secondary or, preferably,tertiary nitrogen atom in an aliphatic chain or else in a heterocyclicring. Of the anthraquinone dyes especially those are suited whichcontain a hydrocarbon group of the formula wherein n equals 14, and Xdenotes one of the following groups: C H N; a)2; 2)a aZ Theseanthraquinone derivatives can be manufactured by reactingaminoanthraquinones which contain a reactive halogen atom, an N02 or OHgroup, with compounds which contain in an aliphatic chain or in aheterocyclic ring at least a secondary, but preferably a tertiary,nitrogen group.

Furthermore, these compounds must contain a group capable of reactingwith the substituted anthraquinone, e.g., an OH group, an NH group or ahalogen atom.

Accordingly the following compounds are to be considered, amongstothers: pyridine-Z-carbinol; pyridine-2- 3,401,003 Patented Sept. 10,1968 ethanol; 4-pico1ylamine; 2-picolylchloride; dimethylaminoethanol;N-beta-oxethylpropanediamine-( 1,3); ethanolisopropanolamine;diethylenetriamine; triethylenetetramine; beta-oxethylurea;beta-oxethylthiourea; 3-allyloxy 2 oxypropylamine (l);N-beta-aminoethylmorpholine; and N-beta-oxethylmorpholine.

The aminoanthraquinone radical must be free from acid groups in thenucleus, such as hydroxyl-, carboxylor sulfo-groups. However, it maycontain other substituents, such as halogen or nitro groups. The hairdyes can be mixed with any desired wetting, dispersing and washingagents, preferably however with those which are anionic or nonionic.Suitable wetting, dispersing and Wash ing agents are, e.g.,alkylbenzenesulfates, fatty alcohol sulfates, alkylsulfonates, fattyacid ethan-olamides, ethylene adducts on fatty acids and fatty alcohols.

The fixing quality of the dyes according to the invention remains goodon the hair when admixed with the agents named above and does notdiminish to any practical extent. Therefore, these dyes can bemanufactured in the form of shampoos, particularly cream shampoos, whichfrequently are desirable in practice.

Furthermore, thickeners, such as methylcellulose, starch, higher fattyalcohols, Vaseline, paraffin oil, fatty acids; also essential oils andhair grooming agents, e.g., pantothenic acid and cholesterol, can beadmixed.

The additives are employed in the customary quantities. For the wetting,dispersing and washing agents, amounts from 0.5 to 30 percent by weight,and for thickeners amounts of 0.1 to 25 percent, by weight, allcalculated on the total composition, are used. The concentration of thedyestuffs according to the invention in the mixtures, depending upon enduse, ranges up to 5 percent by weight of the total composition,preferably 0.l to 2 percent.

Finally, permanent waving agents, lrnown per se, also can be admixed tothe novel hair dyeing agents. These permanent waving materials are basedon compounds containing mercapto groups, e.g., thioglycolic acid,thiolactic acid, mercaptopropaneor mercaptobutanesulfonic acid. Thenovel hair dyes can be produced with these additives since the dyes havethe advantage of stability even in the presence of the materials namedso that storage presents no problem, even over prolonged periods oftime.

Human hair can be dyed with these novel hair dyeing agents without theaid of heating caps or similar devices since temperatures below 40 C.,and preferably room temperature, are required for the dyeing process.The pH of the agents may range from 7 to 10, preferably from 8.5 to 9.5.The agents can be used for dyeing naturally grey hair or for redyeingdyed hair from one color to another. The hair thus dyed. is not affectedby repeated washing nor -by rubbing or other friction. When a permanentwave treatment is imparted to hair dyed with the agents according tothis invention, a change in color or hue does not occur. Finally, thefixing of the color on the hair is very good.

The invention now will be further illustrated by the following examples.However, it should be understood that this is given merely by way ofexplanation, and not of limitation, and that numerous changes may bemade in the details without departing from the spirit and the scope ofthe invention as hereinafter claimed.

All parts given in the examples are parts by Weight, temperatures aredegrees centigrade.

EXAMPLE 1 27.2 parts 1,4-diamino-2-chloroanthraquinone were stirred withparts pyridine-Z-ethanol and 4.4 parts powdered NaOH for 8 hours at 100and for another 16 hours at The excess pyridine-Z-ethanol then wasvacuum-distilled, the crude reaction mixture stirred with 100 partswater and suction-filtered. The residue was treated for 10 minutes at 98with 2,500 parts water and 75 parts concentrated HCl, suction-filteredat 20 and dried. 23 parts of a blue powder were obtained having amelting point of 193202 and having the following structure (Formula 1):

O NH:

1 part of the 1,4-amino-2-[2'-pyridine]-ethoxy)-anthraquinone thusobtained was worked into a shampoo cream, in the following manner: 4.5parts cetyl alcohol, 4.5 parts stearyl alcohol, 1.5 parts fatty alcoholmixture (C -C and parts fatty alcohol sulfate (C -C were heated at 98,the dye added, the mixture emulsified with enough water to make 95 partsand cooled to room temperature with agitation. The pH was adjusted to9.5 with ammonia, and the mixture made up to 100 parts of water. Thecream thus obtained produced a strong and clear red color on naturallygrey hair at 25 when applied for approximately minutes. Ensuingshampooing of the hair did not diminish the red color.

EXAMPLE 2 28.4 parts 1,4-diamino-5-nitroanthraquinone were dissolved in150 parts dimethylformamide, 10.8 parts 4-pieolylamine and 4.4 partspowdered NaOH added, and the mixture stirred for 12 hours on a bath of atemperature of 100. The solvent then was vacuum-distilled, the residuestirred in water, neutralized with dilute acetic acid, andsuction-filtered. After drying, 24.8 parts of a blue dye stuff wereobtained having a melting point of l85-186 and the Formula 2:

1 part of this dyestutf was worked into a cream in the following manner:5 parts each of cetyl and stearyl alcohol, 2 parts wool fat and 12 partsfatty alcohol sulfate (C C were heated at 98, the dye added, the mixtureemulsified with water to make 95 parts and cooled with agitation to roomtemperature. After adjustment of the pH to 7, the mixture was made up to100 parts with water. The cream thus produced dyed naturally grey hair astrong blue within 20 minutes at EXAMPLE 3 1 part of this dye was mixedinto a washing cream as described in the preceding example, except thatthe pH was adjusted to 8. Grey hair treated with the resultant cream iat room temperature attained a strong blue color with a slight red hue.

EXAMPLE 4' 34 parts 1,4-diamino-S-nitroanthraquinone and 135 partsN-beta-oxethylpropanediamine-( 1,3) were reacted at 30 for 15 hours, andwere allowed to stand for another 48 hours at room temperature. Incontrast to the preceding example, no additon of NaOH was made.Thereafter, the reaction mixture was poured into 500 parts ice water,suction-filtered and dried. 33 parts of blue powder of Formula 4 thuswere obtained:

1 part of this dye was incorporated in a hair wash cream as described inExample 1. Naturally grey hair dyed therewith assumed a blue color.

EXAMPLE 5 O NH:

i C H :1

| O NH2 Naturally grey hair treated with a hair wash cream as describedin Example 1 but containing dye (5) produced strongly red hair at 25within 20 minutes.

EXAMPLE 6 14.2 parts 1,4 diamino S-nitroanthraquinone were reacted with100 parts diethylenetriamine at for 15 hours. The reaction mixture waspoured into 1000 parts water and suction-filtered. After drying at 60 invacuo, 15 parts of a dark blue powder were obtained having the Formula6:

1 part of this dye was mixed into a hair wash cream as described inExample 1, except that the pH was adjusted to 9.5. Grey hair treatedwith this cream attained a clear blue color.

EXAMPLE 7 14.2 pants 1,4 diamino S-nitroanthraquinone were reacted wtih7.1 parts ;3oxethylthiourea (respectively 6.8 parts ,B-oxethylurea) and2.4 parts powdered NaOH in 100 parts benzene at for 10 hours. Benzenewas: removed in vacuo, the residue was treated with diluted HCl andsuction-filtered. 15 parts of a blue powder were obtained having thefollowing constitution as shown in Formula 7 respectively 8:

Grey hair dyed with (H. cream containing one of these two dyestuffs at apH of 9 attained a blue color with a slight red hue.

The times named in the preceding examples for application .of the agentsmerely are illustrative, and application times of to 30 minutes can beemployed.

We claim as our invention:

1. 1,4-diaminoanthraquinone free of hydroxyl-, carboxyland sulfo-groupsin the anthraquinone ring; a hydrogen atom in said ring being replacedby an atom selected from the group consisting of oxygen and nitrogen;said atom being linked to a group- O NH:

N AOocIhCIb-Q I O NH2 NH: O

wherein n is a Whole number from 1 to 4 and X is selected from the groupconsisting of -C H N; -N(CH -NHCO-NH and NI-I-CSNH 5. A process for thedyeing of human hair which comprises applying to said hair forapproximately 15 to 30 mintues and substantially at room temperature acream having as the active ingredient 0.1 to 5 percent by weight,calculated on total composition, of 1,4-diaminoanthnaquinone free ofhydroxyl-, carboxyland su1fo-groups in the anthraquinone ring; ahydrogen in said ring being replaced by an atom selected from the groupconsisting of oxygen and nitrogen; said atom being linked to a groupwherein n is a whole number from 1 to 4 and X is selected from the groupconsisting of -C H N; -N(CH -NH-CONH and -NHCS-NH References CitedUNITED STATES PATENTS 3,123,605 3/1964 Turetzky et a1. 260-377 X3,125,586 3/1964 Katz et a1 260-377 3,192,117 6/1965 Kaiser et a1.167-88 3,232,934 2/1966 Hoare 260-379 X FOREIGN PATENTS 807,241 1/ 1959Great Britain.

ALBERT T. MEYERS, Primary Examiner.

V. C. CLARKE, Assisnmt Examiner.

